CN100413844C - Multiple photon absorptive phenyl fluorene derivative and its preparing method - Google Patents

Abstract

The pesent invention relates to a multiple photon absorption phenyl fluorene derivative and a preparation method thereof. The phenyl fluorene derivative has a general formula (I), wherein R stands for C2 to C12 straight-chain or branched-chain alkyl; D stands for an amine group. The compound has greater multiphoton absorption cross section.

Description

Multiphoton absorption phenyl fluorene derivatives and preparation method thereof

Technical field

The present invention relates to multiphoton absorption, particularly a kind of multiphoton absorption phenyl fluorene derivatives and preparation method thereof.

Background technology

The multiphoton absorption process is a research focus of sphere of learning always.As far back as 1931,

-Mayer has just foretold the existence of multiphoton absorption process, reference: [1] in theory

-Mayer, M.Ann.Phys, 1931,9:275-294.Owing to have high spatial modulation performance, the multiphoton absorption process can be widely used in three dimensional optical information storage, reference: [2] B.H.Cumpston, S.P.Ananthavel, Stephen Barlow et al.Nature, 1999,398:51-54; Reference: [3] Parthenopoulos D A, Rentzepis P M.Science, 1989,245:843-845, two-photon fluorescence excitation microscope, reference: [4] Denk W.Strickler J.H., Webb W.W.Science, 1990,248:73-76, frequency upconversion laser, reference: [5] He G S, Yuan L, et al.J.Apply.Phys, 1997,81 (6): 2529-2537; Reference: [6] He G S, Xu G C, et al.Opt.Lett, 1995,20 (5): 435-437, light amplitude limit and light fixed ampllitude, reference: [7] Spangler C W.J.Mater.Chem., 1999,9:2013-2020, three-dimensional little processing, reference: [8] Zhou W, KueblerS M, et al.Science, 2002,296:1106-1109, the medical treatment of light power, reference: [9] Fisher A MR, Murphree A L, Gomer C J.Laser surge Med, 1995, aspects such as 17:2-31.Thereby research and exploitation have the stability height, the big organic materials in multiphoton absorption cross section becomes hot research in recent years.

Summary of the invention:

Purpose of the present invention just provides a kind of multiphoton absorption phenyl fluorene derivatives and preparation method thereof, and this compounds has bigger multiphoton absorption cross section.

Technical solution of the present invention is as follows:

A kind of multiphoton absorption phenyl fluorene derivatives is characterized in that this derivative has following general formula (I):

Wherein: R represents C ₂～C ₁₂The alkyl of straight or branched;

D represents the amine groups derived from following amino-complex:

The synthetic method of described multiphoton absorption phenyl fluorene derivatives is characterized in that this method is:

At first react by Suzuki, phenyl ring is connected to the both sides of fluorenes ring, by bromination reaction bromine is connected on the phenyl ring, then with the amino-complex that contains amine groups under the katalysis of copper catalyst, the Ullmann condensation reaction takes place, make the nitrogen-atoms of amine groups substitute the bromine a series of compound of generation that links to each other with phenyl ring, its general formula of molecular structure is as follows:

The concrete synthesis step of this method is as follows:

1. the dibromo fluorenes is that alkylated reaction and the bromination reaction that passes through the fluorenes ring makes, and its reaction formula is:

2. obtain to contain the compound of amine groups;

3. by Suzuki reaction, phenyl ring is connected to the both sides of fluorenes ring, its reaction formula is:

4. by bromination reaction bromine is connected on the phenyl ring, its reaction formula is:

5. the generation of final compound is to make by the Liv Ullmann condensation reaction, and its reaction formula is:

Technique effect of the present invention:

The present invention designs and has synthesized a class multiphoton absorption phenyl fluorene derivatives dyestuff, and its solubility property in usual vehicle (as normal hexane, chloroform, tetrahydrofuran (THF), methylene dichloride etc.) is good, easy to use.This dyestuff sends fluorescence easily, can be used as luminescent material with polymkeric substance, and this dyestuff has bigger multiphoton absorption cross section, can carry out other application such as three-dimensional storage, Excited Fluorescence Combined microscope, frequency upconversion laser and light amplitude limit.

Description of drawings

Fig. 1: be 2,7-two [4-(dimethylamine) phenyl]-9,9-two (2-ethylhexyl) fluorenes be at N, the light amplitude limit curve in the dinethylformamide solution.

Embodiment

Can further be well understood to the present invention below by specific embodiment, but they not limitation of the invention.

Embodiment 1:2,7-two [4-(pentanoic) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

＜1〉step 1: 9,9-two (2-ethylhexyl) fluorenes synthetic

(34 restrain, and 0.205mol), (56 restrain potassium hydroxide, 1.0mol) with fluorenes, (3.4 grams 0.02mol) join among the 150ml DMSO potassiumiodide, and stirring and dissolving dropwise adds (2-ethylhexyl) bromine (96ml then, 103.5 gram 0.536mol), makes temperature rise to 25 ℃, stirs 24 hours.Reaction is poured mixture in the water into after finishing, and separation, washing, dry back concentrate, and reducing pressure down then, distillation obtains crude product.Analyse further purification at the silica gel upper colonnade and obtain 9,9-two (2-ethylhexyl) fluorenes, 74.4 grams, productive rate 93%.

＜2〉step 2: 2,7-two bromo-9, (0.12 gram 0.47mmol) joins in the 170ml methylene dichloride the synthetic iodine of 9-two (2-ethylhexyl) fluorenes, stirs.With bromine (5.18ml, 0.1mol) molten in the 20ml methylene dichloride, join then in the reaction mixture, at room temperature stirring reaction is 20 hours.After reaction finishes, be that 15% aqueous solution of sodium bisulfite joins in the mixture, stirred the separation organic layer 30 minutes weight percent, washing is dry, filtering and concentrating, and underpressure distillation obtains 2,7-two bromo-9,9-two (2-ethylhexyl) fluorenes, 21.4 grams, productive rate 83%.

＜3〉step 3: 2,7-phenylbenzene-9,9-two (2-ethylhexyl) fluorenes synthetic

With above-mentioned steps＜2〉in the preparation 2,7-two bromo-9,9-two (2-ethylhexyl) fluorenes (0.55 the gram, 0.001mol), phenyl-boron dihydroxide (0.285 the gram, 0.0023mol), (PPh ₃) ₄(0.012 gram 0.01mmol) is dissolved in the 5ml toluene Pd (0), under nitrogen protection, adds the Na of 3ml 2M ₂CO ₃Solution refluxed 48 hours, and after the reaction end, cool to room temperature extracts three times with benzene, and water washes several times then, decompression, distillation, separation, concentrated.Crude product is analysed further purification at the silica gel upper colonnade and is obtained 2,7-phenylbenzene-9,9-two (2-ethylhexyl) fluorenes, 0.35 gram, productive rate 65%.

＜4〉step 4: 2,7-two (4-bromophenyl)-9,9-two (2-ethylhexyl) fluorenes synthetic

With above-mentioned steps＜3〉in the preparation 2,7-phenylbenzene-9,9-two (2-ethylhexyl) fluorenes (0.74 gram, 1.36mmol) be dissolved in 10ml 1: 1 the chloroform and acetic acid, (0.48 restrains, and 2.72mmol), mixture at room temperature stirs a night to add NBS then, reaction finishes the back chloroform extraction, reduces pressure, distills, separates, concentrates.Crude product is analysed further purification at the silica gel upper colonnade and is obtained 2,7-two (4-bromophenyl)-9,9-two (2-ethylhexyl) fluorenes, 0.76 gram, productive rate 80%.

＜5〉step 5: 2,7-two (4-(pentanoic) phenyl)-9,9-two (2-ethylhexyl) fluorenes synthetic

With above-mentioned＜5〉prepare in the step 2; 7-two (4-bromophenyl)-9; 9-two (2-ethylhexyl) fluorenes (7.00g, 0.01mol) molten in 1,2 dichlorobenzene of 25-30ml; under ambient temperature, add salt of wormwood (13.75g; 0.1mol), potassiumiodide (3.83g, 0.023mol); copper (2.68g; 0.042mol), cupric iodide (2.0g, 0.105mol); hexaoxacyclooctadecane-6-6 (1.27g; 0.0048mol), solution becomes orange, adds pentanoic (8.48g then; 0.05mol), 180 ℃ were reacted 2 days under nitrogen protection.Reaction finishes postcooling to room temperature, decompression, distillation, separate, washing, dry, concentrate.Crude product is analysed further purification at the silica gel upper colonnade and is obtained 2,7-two (4-(pentanoic) phenyl)-9,9-two (2-ethylhexyl) fluorenes, 4.03 grams, productive rate 46%.

Embodiment 2:2,7-two [4-(pentanoic) phenyl]-9,9-two (2-ethyl) fluorenes synthetic

＜1〉step 1: 9,9-diethyl fluorenes synthetic

This step is with the step 1 in the example 1, and different is changes (2-ethylhexyl) bromine into monobromethane (40ml, 58.4 grams 0.536mol), obtain 9,9-diethyl fluorenes, 43.26 grams, productive rate 95%.

＜2〉step 2: 2,7-two bromo-9,9-diethyl fluorenes synthetic

This step is with the step 2 in the example 1, and different is with 9, and 9-two (2-ethylhexyl) fluorenes changes 9 into, and (10.44 grams 0.047mol), obtain 2 to 9-diethyl fluorenes, 7-two bromo-9,9-diethyl fluorenes, 15.2 grams, productive rate 85%.

＜3〉step 3: 2,7-phenylbenzene-9,9-two (2-ethyl) fluorenes synthetic

This step is with the step 3 in the example 1, and different is with 2,7-two bromo-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-two bromo-9, (0.38 gram 0.001mol), obtains 2 to 9-two (2-ethyl) fluorenes, 7-phenylbenzene-9,9-two (2-ethyl) fluorenes, 0.24 gram, productive rate 65%.

＜4〉step 4: 2,7-two (4-bromophenyl)-9,9-two (2-ethyl) fluorenes synthetic

This step is with the step 4 in the example 1, and different is with 2,7-phenylbenzene-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-phenylbenzene-9, (0.51 gram 1.36mmol), obtains 2 to 9-two (2-ethyl) fluorenes, 7-two (4-bromophenyl)-9,9-two (2-ethyl) fluorenes, 0.58 gram, productive rate 80%.

＜5〉step 5: 2,7-two (4-(pentanoic) phenyl)-9,9-two (2-ethyl) fluorenes synthetic

This step is with the step 5 in the example 1, different is with 2,7-two (4-bromophenyl)-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-two (4-bromophenyl)-9, (5.32g 0.01mol), obtains 2 to 9-two (2-ethyl) fluorenes, 7-two (4-(pentanoic) phenyl)-9,9-two (2-ethyl) fluorenes, 3.26 grams, productive rate 46%.

Embodiment 3:2,7-two [4-(pentanoic) phenyl]-9,9-two (2-dodecyl) fluorenes synthetic

＜1〉step 1:9,9-two (dodecyl) fluorenes synthetic

This step is with the step 1 in the example 1, and different is changes (2-ethylhexyl) bromine into lauryl bromide (130ml, 133.6 grams 0.536mol), obtain 9,9-two (dodecyl) fluorenes, 104 grams, productive rate 90%.

＜2〉step 2: 2,7-two bromo-9,9-two (dodecyl) fluorenes synthetic

This step is with the step 2 in the example 1, and different is with 9, and 9-two (2-ethylhexyl) fluorenes changes 9 into, and (23.62 grams 0.047mol), obtain 2 to 9-two (dodecyl) fluorenes, 7-two bromo-9,9-two (dodecyl) fluorenes, 25.46 grams, productive rate 82%.

＜3〉step 3: 2,7-phenylbenzene-9,9-two (2-dodecyl) fluorenes synthetic

This step is with the step 3 in the example 1, and different is with 2,7-two bromo-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-two bromo-9, (0.66 gram 0.001mol), obtains 2 to 9-two (2-dodecyl) fluorenes, 7-phenylbenzene-9,9-two (2-dodecyl) fluorenes, 0.42 gram, productive rate 65%.

＜4〉step 4: 2,7-two (4-bromophenyl)-9,9-two (2-dodecyl) fluorenes synthetic

This step is with the step 4 in the example 1, and different is with 2,7-phenylbenzene-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-phenylbenzene-9, (0.89 gram 1.36mmol), obtains 2 to 9-two (2-dodecyl) fluorenes, 7-two (4-bromophenyl)-9,9-two (2-dodecyl) fluorenes, 0.88 gram, productive rate 80%.

＜5〉step 5: 2,7-two (4-(pentanoic) phenyl)-9,9-two (2-dodecyl) fluorenes synthetic

This step is with the step 5 in the example 1, different is with 2,7-two (4-bromophenyl)-9, and 9-two (2-ethylhexyl) fluorenes changes 2 into, 7-two (4-bromophenyl)-9, (8.12g 0.01mol), obtains 2 to 9-two (2-dodecyl) fluorenes, 7-two (4-(pentanoic) phenyl)-9,9-two (2-dodecyl) fluorenes, 4.55 grams, productive rate 46%.

Embodiment 4:2,7-two [4-(N-carbazole) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into the N-carbazole (8.36g, 0.05mol).Productive rate 45%.

Embodiment 5:2,7-two [4-(dimethylamine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into dimethylamine (2.25g, 0.05mol).Productive rate 53%.

Embodiment 6:2,7-two [4-(diethylamine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into diethylamine (3.66g, 0.05mol).Productive rate 53%.

Embodiment 7:2,7-two [4-(dibutylamine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into dibutylamine (6.46g, 0.05mol).Productive rate 53%.

Embodiment 8:2,7-two [4-(pyrrolidyl) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into tetramethyleneimine (3.56g, 0.05mol).Productive rate 53%.

Embodiment 9:2,7-two [4-(methyl (hydroxyethyl) amine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into methyl (hydroxyethyl) amine (3.76g, 0.05mol).Productive rate 53%.

Embodiment 10:2,7-two [4-(ethyl (hydroxyethyl) amine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into ethyl (hydroxyethyl) amine (4.46g, 0.05mol).Productive rate 53%.

Embodiment 11:2,7-two [4-(N-phenyl-1-naphthylamine) phenyl]-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into the N-phenyl-1-naphthylamine (10.96g, 0.05mol).Productive rate 44%.

Embodiment 12:2,7-two [4-([4-methoxy diphenylamine] phenyl)-9,9-two (2-ethylhexyl) fluorenes synthetic

Step is with example 1, different is with the pentanoic in the step 5 change into the 4-methoxy diphenylamine (9.96g, 0.05mol).Productive rate 46%.

Embodiment 13: the measurement of three-photon absorption cross

Consider that according to the theory that three-photon absorbs the non-linear transmitance of three-photon absorbing medium can be written as:

$T^{\′}=\frac{I\left(z\right)}{I_0}=1/\sqrt{(1+2\mathrm{\γz}{I}_0^2)}---\left(1\right)$

Here I ₀Be incident intensity, I _(z)Be transmitted light intensity, z is a sample thickness, and γ is the three-photon uptake factor, and unit is cm ³/ W ²And the concentration d of three-photon uptake factor γ and solution example ₀(M/L) pass is:

γ＝σ ₃N _Ad ₀×10 ^-3(2)

Here σ ₃Be the three-photon absorption cross, unit is cm ⁶/ W ², N _ABe the A Fujiadeluo constant.In the other document, the three-photon absorption cross is defined as again:

σ′ ₃＝σ ₃(hv) ²(3)

Here hv is the photon energy of excitation beam, σ ₃' unit is cm ⁶s ²In this experiment, light source is for transferring Q Nd:YAG pulse laser system, and output optical maser wavelength is 1064nm, pulsewidth 38ps, and repetition rate is 10Hz, measuring result sees the following form

Although the present invention has been done detailed explanation and has quoted some specific embodiments as proof, to those skilled in the art, only otherwise leaving the spirit and scope of the present invention can be obvious as various changes and modifications.

Claims (3)

1. multiphoton absorption phenyl fluorene derivatives is characterized in that this derivative has following general formula (I):

Wherein: R represents C ₂～C ₁₂The alkyl of straight or branched;

D represents the amine groups derived from following amino-complex:

2. the synthetic method of the described multiphoton absorption phenyl of claim 1 fluorene derivatives is characterized in that this method is:

At first react by Suzuki, phenyl ring is connected to the both sides of fluorenes ring, by bromination reaction bromine is connected on the phenyl ring, then with the amino-complex that contains amine groups under the katalysis of copper catalyst, the Ullmann condensation reaction takes place, make the nitrogen-atoms of amine groups substitute the bromine a series of compound of generation that links to each other with phenyl ring, its general formula of molecular structure is as follows:

R represents the straight or branched alkyl group of 2-12 carbonatoms in the structural formula; D represents the amine groups derived from following amino-complex:

3. the synthetic method of multiphoton absorption phenyl fluorene derivatives according to claim 2 is characterized in that the concrete synthesis step of this method is as follows:

1. the dibromo fluorenes is that alkylated reaction and the bromination reaction that passes through the fluorenes ring makes, and its reaction formula is:

2. obtain to contain the compound of amine groups;

3. by Suzuki reaction, phenyl ring is connected to the both sides of fluorenes ring, its reaction formula is:

4. by bromination reaction bromine is connected on the phenyl ring, its reaction formula is:

5. the generation of final compound is to make by the Liv Ullmann condensation reaction, and its reaction formula is:

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